Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of function silica nano material, preparation method and application thereof, this function silica nano material can be used as adsorbent, dye wastewater treatment using more fast and effectively, containing simultaneously a large amount of quaternary ammonium salts in the function silica nano material, to make its adsorption capacity affected by pH value of solution less, can in wider pH scope, use, and easily separate with the aqueous solution.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of function silica nano material QPEI/SiO
2, its structural representation formula is:
In the formula:
Be nanometer SiO
2
Function silica nano material PEI/SiO
2Application as adsorbent.
A kind of preparation method of function silica nano material may further comprise the steps:
The surface modification of A, silica nano material: silica nano material is dispersed in the alcohol, measure an amount of γ-chloropropyl triethoxysilane, add in the reaction vessel, stir, be heated to more than the pure boiling point, constant temperature back flow reaction 8 ~ 12 h make chloropropyl be coupling in the silica nano material surface; After reaction is finished, centrifugation, and advance washing with alcohol, the product after the washing is dry to be processed, and obtains the silica nano material of chloropropylation, i.e. CP/SiO
2Nano material; The mass ratio of silica nano material, γ-chloropropyl triethoxysilane, alcohol is: 1:(0.5 ~ 1): (6 ~ 8), described silica nano material granularity is 90 ~ 150nm, described freeze-day with constant temperature temperature is 100 ~ 150 ℃, and be 12 ~ 24 h drying time;
The silica nano material grafting polyethylene imine of B, surface modification, polymine is abbreviated as PEI: the silica nano material of chloropropylation is distributed in the water, add an amount of PEI, mixed liquor is heated, back flow reaction, reaction finish rear to the reactant liquor centrifugation, and washing sample, remove residual PEI, obtain PEI/SiO after the drying
2Nano material; Described back flow reaction condition is: 90 ~ 100 ℃ of back flow reaction 10 ~ 12 h, and the silica nano material of described surface modification, the PEI concentration in mixed liquor is respectively: 0.1 ~ 0.15 g/g and 0.2 ~ 0.3 g/g; Baking temperature is 60 ~ 100 ℃, and be 8 ~ 12 h drying time;
C, QPEI/SiO
2Synthesizing of nano material, QPEI refers to quaternised PEI: with the PEI/SiO that makes
2Nano material adds an amount of expoxy propane, stirs to be warming up to more than the expoxy propane boiling point after lower ice bath reacts 6 ~ 10 h, steams unreacted expoxy propane, namely gets the PEI/SiO of tertiary amine
2An amount of alcohol is poured into the PEI/SiO of tertiary amine
2In, add an amount of benzyl chloride, under 50 ~ 70 ℃, carry out back flow reaction 18 ~ 24 h, after reaction finishes, filter, with alcohol washing product, drying namely gets QPEI/SiO
2Material; Described PEI/SiO
2The mass ratio of nano material and expoxy propane is 1:(4 ~ 6), the PEI/SiO of described alcohol, tertiary amine
2,, benzyl chloride mass ratio be (2 ~ 3): 1:(1 ~ 2); Described drying condition is more than 60 ~ 100 ℃ of lower dry 24 h;
Single nanometer silicon dioxide particle can react with several organic molecules, some polymer chains of participating in reaction in the above reaction equation.
Alcohol is selected from one or more in methyl alcohol, ethanol, propyl alcohol, the ethylene glycol among described steps A, the C.
Silica nano material can prepare by the following method in the described steps A:
(1), get an amount of alcohol, water, ammoniacal liquor and mix, make mixed liquor;
(2), add an amount of ethyl orthosilicate (TEOS) in the mixed liquor, 10 ~ 40 ℃ of reaction 6 ~ 10 h leave standstill centrifugation after a period of time with reactant liquor, drying makes silica nano material.
Alcohol, water, ammonia (NH in the described step (1)
3) mass ratio be (50 ~ 70): (8 ~ 10): 0.5, the concentration of ethyl orthosilicate (TEOS) in mixed liquor is 0.025 ~ 0.03 g/g in the step (2), drying condition is 50 ~ 90 ℃ of drying 6 ~ 10 h.
Existing adsorbent major part on the rate of adsorption of anionic dye slow and adsorption capacity affected by pH larger, only can in certain pH scope, use.The present invention is to be carrier surface grafting polymer ammonium with silica nano material, make can be in wider pH range the adsorbent of quick adsorption methyl orange.The present invention combines the advantage of silica nano material and macromolecular material, makes the quaternary ammonium functional group relatively concentrated at adsorbent surface, forms a large amount of duplets, more fast and effectively dye wastewater treatment using with anionic dye (such as methyl orange).Containing a large amount of quaternary ammonium salts in this adsorbent, to make its adsorption capacity affected by pH value of solution less.Solve traditional adsorbent adsorption time and grown and be only applicable to the shortcoming of pH narrow range.Therefore, this adsorbent can use in wider pH scope.
The specific embodiment
Embodiment 1
A kind of function silica nano material QPEI/SiO
2, its structural representation formula is:
In the formula:
Be nanometer SiO
2
A kind of preparation method of function silica nano material comprises step:
The surface modification of A, silica nano material: be that the silica of 100 nm is dispersed in the methyl alcohol with granularity, measure an amount of γ-chloropropyl triethoxysilane, add in the there-necked flask, wherein the mass ratio of silica nano material, γ-chloropropyl triethoxysilane, alcohol is: 1:0.5:6, stir, heating at 66 ℃ of constant temperature back flow reaction 8 h, makes chloropropyl be coupling in the silica nano material surface; After reaction is finished, centrifugation, and advance washing with methyl alcohol, 100 ℃ of drying 12 h of the product constant temperature after the washing obtain the silica nano material of chloropropylation;
The reaction equation of steps A is as follows:
The silica nano material grafting polyethylene imine (PEI) of B, surface modification: the silica nano material of chloropropylation is distributed in the water, add PEI, wherein the silica nano material of surface modification, the PEI concentration in mixed liquor is respectively: 0.1 g/g and 0.2 g/g, mixed liquor is heated, at 90 ℃ of lower back flow reaction 10 h, reaction finishes rear to the reactant liquor centrifugation, and use the methanol wash sample, remove residual PEI, obtain the PEI/SiO2 nano material behind 60 ℃ of drying 8 h;
The reaction equation of step B is as follows:
C, QPEI/SiO
2Synthesizing of nano material: with the PEI/SiO that makes
2Nano material adds an amount of expoxy propane, wherein PEI/SiO
2The mass ratio of nano material and expoxy propane is 1:4, stirs to be warming up to 35 ℃ after lower ice bath reacts 6 h, steams unreacted expoxy propane, namely gets the PEI/SiO of tertiary amine
2An amount of methyl alcohol is poured into the PEI/SiO of tertiary amine
2In, add an amount of benzyl chloride, wherein the PEI/SiO of methyl alcohol, tertiary amine
2,, benzyl chloride mass ratio be 2:1:1; Carry out back flow reaction 18 h under 50 ℃, after reaction finishes, filter, use the methanol wash product, 80 ℃ of lower dry 24 h namely get QPEI/SiO
2Material;
The reaction equation of step C is as follows:
The infrared spectrum of the nanostructure intermediate of embodiment 1 preparation is seen Fig. 1, sees that from Fig. 1 each sample is at 1083 cm
-1There is an extremely strong wide absworption peak at the place.The corresponding SiO in this peak
2The stretching vibration absworption peak of middle Si-O-Si.At 3431 cm
-1The broad peak at place is the absworption peak relevant with the silicon hydroxyl that forms hydrogen bond and adsorbed water, and after chemical modification, this peak weakens to some extent, and at 2953 cm
-1C-H key chattering absworption peak appears in the place, shows nanometer SiO
2Chloropropylation has been realized on the surface, and C-H key chattering absworption peak is strong gradually by a-d by can be observed among the figure, and this is because sample C-H key in grafting PEI and quaternized process increases gradually.Chloropropylation SiO
2With (among the figure 3,4) after the PEI reaction at 1460 cm
-1C-N key stretching vibration absworption peak appears in the place, shows that PEI successfully is grafted to nanometer SiO
2The surface.By among the figure 4 observe sample quaternized after at 1627,1417,696,758 cm
-1The phenyl ring characteristic absorption peak occurs, show that quaterisation has occured the PE I that is grafted on the silica gel, has formed functional material QPEI/SiO
2Quaternary ammonium salt does not have INFRARED ABSORPTION, does not therefore occur corresponding absworption peak in 4.
The QPEI/SiO of embodiment 1 preparation
2Percent grafting see Fig. 2, Fig. 2 is QPEI/SiO
2Thermogravimetric curve, (TGA) measures with thermogravimetric, the initial concentration that can find out the particle thermal decomposition from curve is 215 ℃, final temperature is 550 ℃.QPEI/SiO in this is interval
2The loss in weight be 48%.Therefore as can be known QPEI at SiO
2The percent grafting on surface is 0.48g/g.
Function silica nano material QPEI/SiO
2Application as adsorbent.
The QPEI/SiO of embodiment 1 preparation
2Curve of adsorption kinetics to methyl orange is seen Fig. 3, and the preparation mass concentration is the methyl orange solution of 60 mg/L, places tool plug conical flask, takes by weighing the QPEI/SiO of 0.2 g
2Functional material adds in the solution, constant temperature oscillation, keep T=20 ℃ under this condition, pH=7, respectively in 2 min, 5 min, 10 min, 20 min, 30 min, 40 min, 60 min sampling, after the supercentrifuge centrifugation, adopt the concentration of methyl orange in the determined by ultraviolet spectrophotometry supernatant, draw curve of adsorption kinetics.As can be seen from Figure 3, adsorption time has obvious impact to the absorption of methyl orange.Adsorption rate is very fast in initial a few minutes, and is then slack-off gradually, reaches balance behind 10 min.This is required that equilibration time is compared very of short durationly with other adsorbents, and this is to form duplet because contain a large amount of cations on this adsorbent with the methyl orange that contains anion, therefore can adsorb fast and effectively methyl orange.
The QPEI/SiO of embodiment 1 preparation
2Adsorption capacity see Fig. 4, Fig. 4 is QPEI/SiO
2To the absorption isotherm of methyl orange, be 20 ℃ in temperature, take by weighing respectively 0.1 g adsorbent QPEI/SiO under the pH=7 condition
2, join respectively in the 10 mL methyl orange solutions of variable concentrations constant temperature oscillation, reaction a period of time, make absorption reach balance, centrifugation, then adopt the equilibrium concentration of methyl orange in the determined by ultraviolet spectrophotometry supernatant, be calculated as follows the equilibrium adsorption capacity q of methyl orange
e
In the formula, q
eBe the equilibrium adsorption capacity (g/g) of calcein,
V is liquor capacity (mL),
C
oBe the initial mass concentration (g/L) of methyl orange solution,
C
eBe the mass concentration (g/L) of calcein in the supernatant after the adsorption equilibrium,
M is QPEI/SiO
2The quality of functional material (g).
As can be seen from Figure 4, along with the increase of equilibrium concentration, adsorbance increases gradually, levels off at last balance.Absorption meets Langmuir type mono layer adsorption.With Langmuir adsorption isotherm equation it is carried out match
In the formula: K is the Langmuir absorption constant,
C
eThe methyl orange (mg/L) of equilibrium concentration,
q
eBe the equilibrium adsorption capacity of unit adsorbent, methyl orange,
q
mIt is the high adsorption capacity to methyl orange.
By match, K and q
mMust be worth and be respectively 0.56 L/mg, 105.4 mg/g.
The QPEI/SiO of embodiment 1 preparation
2Adsorbance and pH relation are seen Fig. 5, during methyl orange solution, have set different acid-base values in preparation, namely in the constant situation of other conditions, change pH value of solution, measure its adsorption capacity.Fig. 5 has shown that pH value of solution is to QPEI/SiO
2The impact of absorption property.As can be seen from Figure 5, pH value of solution is to QPEI/SiO
2The impact of absorption property is less, and to be subjected to pH to affect larger situation different from other adsorbents for these.When pH<7, functional material QPEI/SiO
2Increase with the pH value slightly descends to the adsorption capacity of methyl orange, and this is because QPEI/SiO
2By protonated, quaternary ammonium group increases the not quaternised amido N of the part atom that exists on the macromolecular chain of surface on the examination adsorbent, causes QPEI/SiO in acid solution
2Adsorption capacity descend to some extent with the increase of pH.And pH 7 o'clock, adsorption capacity does not increase with pH and changes.
Embodiment 2
A kind of function silica nano material QPEI/SiO
2, the structural representation formula is with embodiment 1.
A kind of preparation method of function silica nano material may further comprise the steps:
The surface modification of A, silica nano material: be that the silica of 120nm is dispersed in the ethanol with granularity, measure an amount of γ-chloropropyl triethoxysilane, add in the there-necked flask, wherein the mass ratio of silica nano material, γ-chloropropyl triethoxysilane, alcohol is: 1:0.5:6, stir, heating at 80 ℃ of constant temperature back flow reaction 10 h, makes chloropropyl be coupling in the silica nano material surface; After reaction is finished, centrifugation, and advance washing with methyl alcohol, 120 ℃ of drying 15 h of the product constant temperature after the washing obtain the silica nano material of chloropropylation;
The silica nano material grafting polyethylene imine (PEI) of B, surface modification: the silica nano material of chloropropylation is distributed in the water, add PEI, wherein the silica nano material of surface modification, the PEI concentration in mixed liquor is respectively: 0.12 g/g and 0.25 g/g, mixed liquor is heated, at 90 ℃ of lower back flow reaction 12 h, reaction finishes rear to the reactant liquor centrifugation, and uses the ethanol washing sample, remove residual PEI, obtain PEI/SiO behind 80 ℃ of drying 10 h
2Nano material;
C, QPEI/SiO
2Synthesizing of nano material: with the PEI/SiO that makes
2Nano material adds an amount of expoxy propane, wherein PEI/SiO
2The mass ratio of nano material and expoxy propane is 1:5, stirs to be warming up to 35 ℃ after lower ice bath reacts 8 h, steams unreacted expoxy propane, namely gets the PEI/SiO of tertiary amine
2An amount of ethanol is poured into the PEI/SiO of tertiary amine
2In, add an amount of benzyl chloride, wherein the PEI/SiO of ethanol, tertiary amine
2,, benzyl chloride mass ratio be 2.5:1:1.5; Carry out back flow reaction 20 h under 60 ℃, after reaction finishes, filter, use the ethanol washed product, 80 ℃ of lower dry 28 h namely get QPEI/SiO
2Material;
The reaction equation of steps A ~ C is with embodiment 1;
Wherein, silica nano material prepares by following steps:
(1), get an amount of alcohol, water, ammoniacal liquor and mix, make mixed liquor, alcohol, water, ammonia (NH
3) mass ratio be 50:8:0.5;
(2), in mixed liquor, add an amount of ethyl orthosilicate (TEOS), 10 ℃ of reaction 10 h leave standstill centrifugation after a period of time, 50 ℃ of drying 10 h with reactant liquor, make silica nano material, the concentration of ethyl orthosilicate (TEOS) in mixed liquor is 0.025 g/g.
Embodiment 3
A kind of function silica nano material QPEI/SiO
2, the structural representation formula is with embodiment 1.
A kind of preparation method of function silica nano material comprises step:
The surface modification of A, silica nano material: be that the silica of 150nm is dispersed in the propyl alcohol with granularity, measure an amount of γ-chloropropyl triethoxysilane, add in the there-necked flask, wherein the mass ratio of silica nano material, γ-chloropropyl triethoxysilane, alcohol is: 1:1:8, stir, heating at 88 ℃ of constant temperature back flow reaction 12 h, makes chloropropyl be coupling in the silica nano material surface; After reaction is finished, centrifugation, and advance washing with propyl alcohol, 150 ℃ of drying 18 h of the product constant temperature after the washing obtain the silica nano material of chloropropylation;
The silica nano material grafting polyethylene imine (PEI) of B, surface modification: the silica nano material of chloropropylation is distributed in the water, add PEI, wherein the silica nano material of surface modification, the PEI concentration in mixed liquor is respectively: 0.15 g/g and 0.3 g/g, mixed liquor is heated, at 100 ℃ of lower back flow reaction 10 h, reaction finishes rear to the reactant liquor centrifugation, and uses the propyl alcohol washing sample, remove residual PEI, obtain PEI/SiO behind 100 ℃ of drying 10 h
2Nano material;
C, QPEI/SiO
2Synthesizing of nano material: with the PEI/SiO that makes
2Nano material adds an amount of expoxy propane, wherein PEI/SiO
2The mass ratio of nano material and expoxy propane is 1:6, stirs to be warming up to 35 ℃ after lower ice bath reacts 10 h, steams unreacted expoxy propane, namely gets the PEI/SiO of tertiary amine
2An amount of propyl alcohol is poured into the PEI/SiO of tertiary amine
2In, add an amount of benzyl chloride, wherein the PEI/SiO of propyl alcohol, tertiary amine
2,, benzyl chloride mass ratio be 3:1:2; Carry out back flow reaction 24 h under 70 ℃, after reaction finishes, filter, use the propyl alcohol washed product, 100 ℃ of lower dry 24 h namely get QPEI/SiO
2Material;
The reaction equation of steps A ~ C is with embodiment 1
Wherein, silica nano material prepares by following steps:
(1), get an amount of alcohol, water, ammoniacal liquor and mix, make mixed liquor, alcohol, water, ammonia (NH
3) mass ratio be 60:9:0.5;
(2), in mixed liquor, add an amount of ethyl orthosilicate (TEOS), 40 ℃ of reaction 6 h leave standstill centrifugation after a period of time, 80 ℃ of drying 8 h with reactant liquor, make silica nano material, the concentration of ethyl orthosilicate (TEOS) in mixed liquor is 0.028 g/g.
Embodiment 4
A kind of function silica nano material QPEI/SiO
2, the structural representation formula is with embodiment 1.
A kind of preparation method of function silica nano material comprises step:
The surface modification of A, silica nano material: be that the silica of 110 nm is dispersed in the ethylene glycol with granularity, measure an amount of γ-chloropropyl triethoxysilane, add in the there-necked flask, wherein the mass ratio of silica nano material, γ-chloropropyl triethoxysilane, alcohol is: 1:1:8, stir, heating at 198 ℃ of constant temperature back flow reaction 12 h, makes chloropropyl be coupling in the silica nano material surface; After reaction is finished, centrifugation, and spent glycol advances washing, 150 ℃ of drying 24 h of the product constant temperature after the washing obtain the silica nano material of chloropropylation;
The silica nano material grafting polyethylene imine (PEI) of B, surface modification: the silica nano material of chloropropylation is distributed in the water, add PEI, wherein the silica nano material of surface modification, the PEI concentration in mixed liquor is respectively: 0.12 g/g and 0.3 g/g, mixed liquor is heated, at 100 ℃ of lower back flow reaction 12 h, reaction finishes rear to the reactant liquor centrifugation, and the spent glycol washing sample, remove residual PEI, obtain PEI/SiO behind 100 ℃ of drying 12 h
2Nano material;
C, QPEI/SiO
2Synthesizing of nano material: with the PEI/SiO that makes
2Nano material adds an amount of expoxy propane, wherein PEI/SiO
2The mass ratio of nano material and expoxy propane is 1:6, stirs to be warming up to 36 ℃ after lower ice bath reacts 10 h, steams unreacted expoxy propane, namely gets the PEI/SiO of tertiary amine
2Proper amount of glycol is poured into the PEI/SiO of tertiary amine
2In, add an amount of benzyl chloride, wherein the PEI/SiO of propyl alcohol, tertiary amine
2,, benzyl chloride mass ratio be 3:1:2; Under 70 ℃, carry out back flow reaction 24 h, after reaction finishes, filter, the spent glycol washed product, 60 ℃ of lower dry 30 h namely get QPEI/SiO
2Material;
The reaction equation of steps A ~ C is with embodiment 1
Wherein, silica nano material prepares by following steps:
(1), get an amount of alcohol, water, ammoniacal liquor and mix, make mixed liquor, alcohol, water, ammonia (NH
3) mass ratio be 70:10:0.5;
(2), in mixed liquor, add an amount of ethyl orthosilicate (TEOS), 30 ℃ of reaction 10 h leave standstill centrifugation after a period of time, 90 ℃ of dry 6h with reactant liquor, make silica nano material, the concentration of ethyl orthosilicate (TEOS) in mixed liquor is 0.03 g/g.